EEE 6404

Diffusion
Ref: R C Jaeger, S M Sze, B O Cui

Diffusion
• Diffusion is a technique to alter the conductivity of a semiconductor (e.g., Si or Ge)
through the introduction of impurity.

• Diffusion is used to form base and emitter regions in bipolar technology and source
and drain regions in MOS technology.

NMOS BJT Base Emitter Collector

p n+ n+
n-
n+

p well

• Dopant atoms can be introduced into Si by diffusion methods like:

a) diffusion from a chemical source in vapor form (high T),
b) diffusion from a doped-oxide source,
c) diffusion and annealing from an ion-implanted layer.

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 Diffusion Mechanism
(In Solids)
• The kinetics of diffusion in solids is
affected by point defects
(vacancies and interstitials) which
are generated at high
temperatures.

• In fact, diffusion in a solid can be

visualized as atomic movement of
the diffusant through the crystal
lattice by vacancies and
interstitials.

• The figure in the bottom shows a

simplified 2D Si lattice structure
(the open circles are lattice atoms
at low temperature positions).
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Diffusion Mechanism
(Vacancy/Substitutional Diffusion)
• At elevated temperature, the
lattice atoms vibrate around the
diffusion by a vacancy
equilibrium lattice sites.
vacancy

• Sometimes, a host atom acquires

sufficient energy to leave the
lattice site and to become an
interstitial atom and creating a
vacancy.

• When a neighboring atom

(host/impurity) migrates to the
vacancy, it is called diffusion by a
vacancy or substitutional diffusion.

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 Diffusion Mechanism
(Self and Impurity Diffusion)

• If the migrating atom is a host

atom, then it is called self-
diffusion.

self-diffusion

• If the migrating atom is an

impurity atom, then it is
called impurity diffusion. impurity diffusion

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Diffusion Mechanism
(Diffusion of Vacancy and Divacancy)
• A vacancy has to diffuse away from
the site that the impurity atom had
just occupied to produce impurity
atom movement.

• There can be diffusion assisted by a

double vacancy or divacancy where
the impurity atom moves to a
second vacancy that is at the
nearest neighbor of the original
vacancy site.

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 Diffusion Mechanism
(Interstitial Diffusion Mechanism)
interstitial
• Movement of an interstitial atom diffusion
(smaller than the host atom) mechanism
without occupying a lattice site is
called the interstitial diffusion
mechanism.

• Activation energies required for

interstitial diffusion are lower than
those required for diffusion by
vacancy.

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Diffusion Mechanism
(Interstitialcy Mechanism )
interstitialcy
mechanism
• An interstitialcy mechanism is an
extended interstitial mechanism.

• It is shown in figure (b), where an

interstitial silicon atom displaces a
substitutional impurity (step 1),
turning it to an interstitial atom
(step 2). Subsequently, the impurity
atom displaces another host atom
(step 3) and the second host atom
becomes a self interstitial (step 4).

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 Diffusion Mechanism
(Different types of Diffusers)

• For dopant impurity diffusion in silicon (e.g., P, B, As, Sb), vacancy and
interstitialcy mechanisms dominate. Typically, P and B diffuse via both
vacancy and interstitialcy mechanisms while As and Sb (along with Ga,
Al) diffuse via vacancy mechanisms. Dopants are relatively slow
diffusers.

• Group I and VIII elements (e.g., Na+, Li+, Fe+) occupy small ionic radii
and they are usually fast diffusers.

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Diffusion Mechanism
Interstitial Diffusion

Impurities that diffuse by interstitial diffusion:

O, Au, Ag, Fe, Cu, Ni, Zn, Mg, Li, H.
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 Diffusion Mechanism
Substitutional (Vacancy) Diffusion

Impurities that diffuse by substitutional (vacancy) diffusion:

As, Al, Ga, Sb.
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Diffusion Equations:
Fick's 1st Law of Diffusion
• Fick’s first law relates the diffusion
flux along a direction to the
concentration gradient.

C ( x, t )
J  D
x
Here
• J is the rate of transfer of solute per
unit area (diffusion flux,
atoms m−2 s−1). J is used to quantify
how fast diffusion occurs.
• C is the concentration of solute
(function of x and t only, atoms/m3)
• x is the direction of solute flow (m)
• t is the diffusion time (s)
• D is the diffusivity (cm2/s)
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 Fick's 1st Law of Diffusion
C ( x, t )
J  D
x
• The diffusion flux is proportional
to the concentration gradient of
the solute.

• The negative sign states that

matters flow in the direction of
decreasing dopant concentration
(the concentration gradient is
negative).

• So, the dopant atoms will diffuse

from a high-concentration region
toward a low-concentration
region.
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Fick's 2nd Law of Diffusion

• Fick's second law predicts how diffusion causes the concentration to
change with time.

• According to Fick's law, the change of solute concentration with time

equals the local decrease of the diffusion flux (in the absence of a source
or a sink); that is

C ( x, t ) J ( x, t )   C ( x, t ) 
  D
t x x  x 
• When the concentration of the solute is low, the diffusivity at a given
temperature can be considered as a constant. So,

C ( x, t )  2C ( x, t )
D Time varying diffusion equation
t x 2
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 Solution of Fick's Equation:
Constant Surface Concentration
(Constant Source Diffusion)
• Solutions for Fick’s 2nd equation can be obtained for various initial
and boundary conditions.

• One of the conditions is the assumption of constant surface

concentration where the impurity concentration is held constant at
the wafer surface during the entire diffusion period. The is also called
the constant source diffusion.

• Here, the initial condition at t=0 is C(x, 0) = 0 meaning the dopant

concentration in the substrate is initially zero.

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Solution of Fick's Equation:

Constant Surface Concentration
• The boundary conditions are C(0, t) = Cs and C(∞, t) = 0 where
• Cs is the surface concentration (in atoms/cm3)
• x is the distance (cm)
• t is the diffusion time (s)

• In the first boundary condition, Cs (at x = 0) is the constant surface

concentration which is independent of time.

• The second boundary condition (at x = ∞) states that there are no

impurity atoms at a large distance from the surface.

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 Solution of Fick's Equation:
Constant Surface Concentration
• The solution (based on the given conditions) is given by
x
C ( x, t )  Cs erfc ( )
2 Dt
where
• erfc stands for the complementary error function
• Dt is the characteristic diffusion length

• The complementary error function erfc(x) is defined as


erfcx   1  erf x    exp -u du
2 2

 x

erfc0  1 erfc  0
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Solution of Fick's Equation:

Constant Surface Concentration Profiles
• The solution suggests that, as time
progresses, the diffusion front proceeds
further into the wafer with the surface
concentration (Cs=N0) remaining
constant.
x
C ( x, t )  Cs erfc ( )
2 Dt

• The total no of impurity atoms in the

silicon per unit area is called the
diffusion dose (Q) which can be found
by
 x 
 
2C
Q   C ( x, t )dx   Cs erfc  dx  s Dt
0 0  2 Dt  
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 Solution of Fick's Equation:
Constant Total Dopant
(Limited Source Diffusion)
• Another solution for Fick’s equation is obtained under the assumption of
constant total dopant.

• It assumes that a fixed (or constant) amount of dopant is deposited onto the
silicon surface (in a thin layer) and then the deposited dopant diffuses into the
silicon (all the dopant atoms remain in the silicon).

• The is also called limited source diffusion or drive-in diffusion.

• Initial condition is: C(x, 0) = 0


• Boundary conditions are:  C ( x, t )dx  QT and C(∞, t) = 0
0

where QT is the diffusion dose (remains constant).

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Solution of Fick's Equation:

Constant Total Dopant
• The solution of the diffusion equation with these conditions is:

QT  x2 
C ( x, t )  exp   
Dt  4 Dt 
• The function represents a gaussian distribution (as opposed to an erfc
curve). Gaussian and erfc curves look similar but erfc curves fall off more
rapidly.

• The surface concentration is obtained from C(x, t) at x=0 and it behaves

as a function of diffusion time (not a constant).
QT
C (0, t ) 
Dt

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 Solution of Fick's Equation:
Constant Total Dopant Profiles
• The dose remains constant throughout the diffusion. So, as the front moves into
the wafer, the surface concentration must decrease (N01>N02>N03) so that the
area under the curve can remain constant.

QT  x2 
C ( x, t )  exp   
Dt  4 Dt 

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Solution of Fick's Equation:

Comparison of ERFC and Gaussian Profiles

x QT  x2 
C ( x, t )  Cs erfc ( ) C ( x, t )  exp   
2 Dt Dt  4 Dt 

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 Solution of Fick's Equation:
Comparison of ERFC and Gaussian Profiles

x
C ( x, t )  Cs erfc ( )
2 Dt

QT  x2 
C ( x, t )  exp   
Dt  4 Dt 

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Two-Step Diffusion
• A two-step diffusion consists of a constant 1. Pre-
source diffusion (predeposition) followed by deposition for
a limited source diffusion (drive-in). dose control

• A shallow diffusion layer is formed under a

constant surface concentration condition in
the silicon (predeposition step) and is 2. Drive in
followed by a drive-in step under a constant
total dopant condition which moves the for profile
diffusion front to the desired depth. control

• The resulting profile is approximated by a Dtdrivein  Dtpredeposition

Gaussian solution if

• And, the profile is approximated by a erfc Dtdrivein  Dtpredeposition

distribution if

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 Temperature Dependence of
Diffusion Coefficient
• Diffusion coefficient of dopants (D) have a strong temperature dependence. They follow the
Arrhenius behavior and depend exponentially on T:

 E 
D  D0 exp   
Here,  kT 
• D0 is a (nearly) temperature independent term that depends on the geometry of the lattice
(in cm2/s).
• E is the activation energy (in eV).

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Temperature Dependence of
Diffusion Coefficient

Substitutional Diffusers (small D): Interstitial Diffusers (large D):

B, P, As, Al, Ga, Sb. Au, Ag, Fe, Cu, Ni, Zn, Mg, Li.

Diffusion for interstitial impurities is difficult to control as they have large diffusion coefficients.
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 Application of Diffusion: C ( x, t )  Cs erfc (
Junction Formation
Cs  N 0

C( x j , t)  N B  N0

QT
C ( x, t )  ex
Dt
QT
 The junction depth for Gaussian 
and erfc distributions is obtained Dt
from the condition:
At x=xj, N(x)=NB. C( x j , t)  N B  N0
 Junction depth:
N 
x j  2 Dt ln  0 
 NB 
N 
EEE 6404
x j  2 Dt erfc 1  B  27
 N0 

Application of Diffusion:
Junction Formation
N  N 
 Junction depth: x j  2 Dt ln  0  x j  2 Dt erfc 1  B 
 NB   N0 
 The Gaussian function is easily evaluated. The erfc function is evaluated graphically with the
figure on the left and the background concentration (NB) is evaluated graphically with the
figure on the right when the wafer is uniformly doped.

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 Diffusion: Example
Problem:
Phosphorus is added to a silicon wafer from a gaseous source at 975oC for 30 minutes. Determine the junction depth for a 0.2
Ω-cm p-type substrate. Assume that the diffusion coefficient of phosphorus is 10-13 cm2 s-1 and that its solid solubility is 1021
cm-3 at 975oC.
Solution:
• As the impurity concentration is held constant at the wafer surface during the diffusion period, the diffusion mechanism is
assumed to be governed by the complementary error function.

Junction depth:
N 
x j  2 Dt erfc 1  B 
 N0 

• Here, D = 10-13 cm2 s-1, surface N0 = 1021 cm-3 at 975oC, Resistivity (p-type substrate) = 0.2 Ω-cm
• So, using figure 1, background NB = NA = 6.3 x 1016 cm-3, NB / N0 = 6.3 x 1016 / 1021 = 6.3 x 10-5
• So, using figure 2, erfc-1(6.3 x 10-5 ) = 2.8
• xj = (2)[(10-13)(1800)]1/2*(2.8) = 7.6 x 10-5 cm = 0.76 μm
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Diffusion Characteristics:
Lateral Diffusion
• Impurities diffuse not only vertically but also laterally during diffusion. The figure
shows normalized two-dimensional ERFC diffusion.

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 Diffusion Characteristics:
Lateral Diffusion
 The figure shows normalized two-dimensional Gaussian diffusion.

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Diffusion Junction Characterization:

Junction Depth Measurement
• Groove and stain method: A cylindrical
groove is mechanically ground into the
surface of the wafer. The radius of the
grinding tool R is known.

• After grooving, the junction is defined by

staining the junction with an etchant. The
etchant uses a mixture of HF and HNO3 and
after staining, p-type silicon typically turns
dark. The stained region is enhanced through
exposure to high intensity light.

• The distances a and b are measured through

a microscope.

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 Diffusion Junction Characterization:
Junction Depth Measurement

•  
x j  a 2  b2 / 2R

• This method is not useful for

xj < 1 μm.

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Diffusion Junction Characterization:

Sheet Resistance Definition

• Sheet resistance (Rs) is a measure

of resistance of thin films that are nominally L L
uniform in thickness. For a diffused layer, Rs R 
eliminates the need to know its profile details. A (Wt )
 L L
 ( )  Rs
• Unit of sheet resistance is Ohm per square t W W
(Ω/□).
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 Diffusion Junction Characterization:
Sheet Resistance Measurement
 The figure shows top and side
views of two dumbbell shaped
resistors.

 They are of different physical sizes

but their L/W ratios and
resistances are equal.

 For each of them, L/W=7.

 End contribution for each end

~0.65 square.

 If, Sheet Resistance

Rs =50 Ω/□,

 Then, resistance of each resistor

=(50*7)+(0.65*2*50)=415 Ω.

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Diffusion Junction Characterization:

Four Point Probe Measurement

• The “Four Point Probe” is a technique to measure bulk resistivity of wafers and sheet
resistance of shallow diffused layers.

• A fixed current (I) is injected by the outer probes and the resulting voltage (V) is
measured by the inner probes. Probe spacing is s and layer thickness is t.

  2s(V / I ) for t  s
  (t / ln 2)(V / I ) for t  s
Rs   / t  ( / ln 2)(V / I ) for t  s
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Diffusion Junction Characterization:
Van der Pauw’s Method
• The “Van der Pauw’s Method” is a
technique to measure sheet resistance of
arbitrarily shaped thin samples by
placing four contacts on the sample
periphery.

• A current (I) is injected through one pair

of contacts and the resulting voltage (V)
is measured across another pair of
contacts.


Rs   / t   (
VCD
)
ln 2 I AB

• For accuracy, the probes are rotated by

90° and the measurement is repeated
three times.
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Diffusion Methods
• The open furnace tube diffusion
system using solid, liquid and
gaseous sources is shown in the
figure.

(a) Solid source in a platinum

source boat in the rear of
diffusion tube

(b) liquid-source system with

carrier gas passing through a
bubbler

(c) diffusion system using gaseous

impurity sources.

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 Diffusion Methods
(Horizontal and Vertical Furnaces)

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Commonly Used Dopants:

Dopant Reactions
• Boron (B) is the most commonly used p type dopant (it can be effectively
masked by SiO2).

• The diffusivity of Al and Ga in SiO2 is high and they cannot be effectively

masked by SiO2.

• P, As and Sb can be masked by SiO2 and they are commonly used as n type
dopants.

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 Commonly Used Dopants:
Boron Reactions
• Boron has high solubility in Si and can achieve an active surface
concentration as high as 4x1020/cm3.

• A surface reaction with boron trioxide (B2O3) is used for introduction of

B to the Si surface:

2B2O3  3Si  4B  3SiO 2

• An excess amount of B2O3 causes a “brown boron skin” formation which

is very difficult to remove with most acids. This is minimized by creating
an oxidizing ambient incorporating 3-10% oxygen. In a two step
diffusion, the B predeposition is followed by a wet oxidation step to
assist boron skin removal.

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Commonly Used Dopants:

Boron Reactions
• Common solid sources of B: trimethylborate (TMB, CH
) and boron O B
nitride.
3 3

• TMB is a solid with high vapor pressure at room temperature and is normally
placed outside the diffusion furnace and cooled below room temperature.

• Vapor of TMB reacts in furnace with oxygen (carrier gas) to form B2O3, CO2 and
H2O.

2CH3O3 B  9O2 900


 C
 B2O3  6CO2  9H 2O

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 Commonly Used Dopants:
Boron Reactions
• Common liquid source for B: boron tribromide (BBr3)

4BBr3  3O2  2B2O3  6Br2

• Free bromine combines easily with metallic impurities and useful for
removing (gettering) metallic impurities during diffusion.

• Primary gaseous source of B: diborane (B2H6). It is highly toxic and

explosive. To ensure safety, diborane is usually diluted with 99.9%
argon or nitrogen. It can be oxidized in O2 and CO2.

B2 H 6  3O2 300
 C
 B2O3  3H 2O
B2 H 6  6CO2  B2O3  6CO  3H 2O

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Commonly Used Dopants:

Summary of Boron Reactions
Surface reaction: 2B2O3  3Si  4B  3SiO2

Solid sources: boron nitride (BN) and trimethylborate (TMB).

2CH 3O3 B  9O2 900

  B2O3  6CO2  9H 2O
o
C

4BN + 3O2  2B2O3 + 2N2

Liquid sources: boron tribromide BBr3.

4 BBr3  3O2  2 B2O3  6Br2
Gaseous sources: diborane B2H6.
B2 H 6  3O2 300
  B2O3  3H 2O
o
C

B2 H 6  6CO2 300
  B2O3  6CO  3H 2O
o
C

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 Commonly Used Dopants:
Phosphorus Reactions
Phosphorus has a higher solubility in silicon than does boron.
Surface concentration in the ~1021/cm3 range can be achieved.

Surface reaction used for introduction of P into Si: 2P O

2 5  5Si  4P  5SiO2
Solid sources (not popular):
Phosphorus pentoxide P2O5
Ammonium monophosphate NH4H2PO4
Ammonium diphosphate (NH4)2H2PO4

Popular diffusion systems use liquid or gaseous P sources.

Liquid source: phosphorus oxychloride POCl3. A carrier gas is passed through
the bubbler and brings the vapor into diffusion furnace. The liberated chlorine
serves as a gettering agent.
4 POCl3  3O2  2 P2O5  6Cl2
Gaseous source: phosphine PH3. It is highly explosive and toxic and supplied
in dilute form with 99.9% argon or nitrogen.

2PH 3  4O2  P2O5  3H 2O

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Commonly Used Dopants:

Arsenic & Antimony Reactions
Arsenic has the highest solubility among common dopants of Si with surface
concentration reaching 2x1021/cm3.

Arsenic surface reaction:

2 As2O3  3Si  3SiO2  4 As

Solid sources: results in low surface concentrations.

Gaseous source: arsine AsH3.

Ion implantation is normally used for As deposition.

Antimony surface reaction:

2Sb2O3  3Si  3SiO2  4Sb

Liquid source: antimony pentachloride Sb3Cl5.

Ion implantation is normally used for Sb deposition.

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 Remember:
Gaseous dopants can be very toxic

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